Nitramides



United States Paten NITRAMIDES Milton B. Frankel, Pasadena, and KarlKlager, Monrovia, Califl, assignors to Aerojet-General Corporation,Azusa, Calif., a corporation of Ohio No Drawing. Filed Oct. 25, 1954,Ser. No. 464,612

8 Claims. (Cl. 260-561) This invention relates to new compositions ofmatter and a method for their preparation. In particular, this inventionrelates to nitramides having the general formula:

wherein R is an alkyl radical and A is an alkylene radical.

Due to their high oxygen content, these compounds are excellent highexplosives. They also find valuable use as oxygen donating additives forpropellant fuels.

The compounds of this invention are prepared by reacting N,N-diacyldinitro diamides with nitric acid, in accordance with the generalreaction scheme set forth below:

wherein R and A are as defined above.

The dinitro diamides used as starting materials in this invention areprepared by condensing dinitro diamines with acyl anhydrides, asdisclosed in assignees copending application Serial No. 210,626, filedFebruary 12, 1951 now abandoned.

To more clearly illustrate this invention, the following example ispresented. It is to be understood, however, that this example ispresented merely as a means of illustration, and is not intended tolimit the scope of the invention in any way.

EXAMPLE I Preparation of N,N'-dinitro-N,N'-diacetyl-3,3-dinitro-1,5-pentane diamine A nitrating mixture of 250 ml. of 100%nitric acid and 250 ml. ofacetic anhydride was cooled to C. and 98.5 gm.(0.36 mole) of N,N-diacetyl-3,3-dinitro-1,5- pentane diamine was added.The solution was stirred for 40 minutes and then poured onto ice. Thecreamcolored solid was collected, washed with water and dried, andrecrystallized from chloroform to give 65.2 gm. (50%) ofN,N'-dinitro-N,N'-diacetyl-3,3-dinitro-1,5-pentane diamine, M.P. 100-101C., exhibiting an impact stability greater than 100 cm./2 kg. Theelemental analysis of the product is as follows:

Calculated for C H N O percent C, 29.51; percent H, 3.85; percent N,22.95. Found: percent C, 29.84; percent H, 3.83; percent N, 23.67.

We have also found that polynitro diamides such asN,N'-dipropanoyl-4,4-dinitro-1,7-heptane diamine, N,N'-dipropanoyl-5,5-dinitro-1,9-nonane diamine, and N,N'-dihexanoyl-6,6-dinitro-1,1l-undecane diamine are readily nitrated withnitric acid to form the corresponding nitramides, namely,N,N'-dinitro-N,N'-dipropanoyl-4,4-dinitro-1,7-heptane diamine,N,N'-dinitro-N,N'-dipropanoyl- 5,5-dinitro-l,9-nonane diamine, andN,N'-dinitro-N,N' dihexanoyl-6,6-dinitro-1,1l-undecane diamine.

It is apparent that any member of this series of nitramides can beprepared by merely selecting the appropriate polynitro diamide andreacting it with nitric acid, in accordance with the teachings of thisinvention.

The nitro compounds of this invention are useful as high explosives andcan be used in any conventional explosive missile, projectile, rocket,or the like, as the main explosive charge. An example of such a missileis disclosed in United States Patent No. 2,470,162, issued May 17, 1949.One way of using the high explosives of this invention in a device suchas that disclosed in United States Patent No. 2,470,162, is to pack thecrystalline explosive in powder form into the warhead of the missile.Alternatively, the crystals can be first pelletized and then packed. Acharge thus prepared is sufficiently insensitive to withstand the shockentailed in the ejection of a shell from a gun barrel or from a rocketlaunching'tube under the pressure devejoped from ignition of apropellant charge, and can be caused to explode on operation of animpactor time fuse-mechanism firing a detonating explosive such as leadazide or mercury fulrninate.

We claim:

1. As new compositions of matter, nitramides having the general formula:

wherein R is a lower alkyl radical and A is a lower alkylene radical.

2. As a new composition of matter, N,N'-dinitro-N,N'-diacetyl-3,3-dinitro-l,5-pentane diamine having the structural formula:

3. The method of preparing nitramides having the general formula:

which comprises reacting N,N'-diacyl-dinitro diamines having the generalformula:

wherein R is a lower alkyl radical and A is a lower alkylene radical,with nitric acid.

4. The method of preparingN,N'-dinitro-N,N'-diacetyl-3,3-dinitro-1,5-pentane diamine whichcomprises reacting N,N-diacetyl-3,3-dinitro-1,5-pentane diamine withnitric acid.

7 3 I V fSrAsanew-"comfioition of matter, N,N'-dinitro-N,N'-dipropanoyl-4;4-dinitro-1;7-heptane diamine having the structuralformula:

g r m, IIIOa .I Ioi 0 tomorrr c-N-cmomonro-cmom N- c-dmomom N0a 6. As anewcomposition of matter, N,N-dinitro-N,N'-'"dipropanoyl-5,5-dinitro-1,9-nonane diamine having the 'structuralformula:

'7. As a new composition ofmatter,,N,N-dinitro N,N'-"dihe'xanoyl-6,6-dinitro-1,1l-undecane diamine having the structuralformula:

N02 NO:

8. l'he method of Preparin nitramlideysihmiing lthe'gtcn eral formula:

which comprises reacting "N,N'-diacyl-dinitro diamines having thegeneral formula:

with nitric acid ran-temperature:ofabout 5 0; wherein R is a lower alkylradical and A is a lower alkylene radical.

' No references cited.

1. AS NEW COMPOSITIONS OF MATTER, NITRAMIDES HAVING THE GENERAL FORMULA: